Photographic processing composition and process comprising cysteine and an aldehyde bisulfite

ABSTRACT

Photographic-processing composition for developing photographic elements in the presence of a developing agent such as hydroquinone, comprising cysteine, an aldehyde bisulfite such as sodium formaldehyde bisulfite and an organic antifoggant. The composition is advantageously employed in a continuous transport processing machine.

United States Patent Frank J. Drago;

Clinton Van Grol, both of Rochester, N.Y. 20,791

Mar. 18, 1970 Oct. 26, 1971 Eastman Kodak Company Rochester, N .Y.

lnventors Appl. No. Filed Patented Assignee PHOTOGRAPHIC PROCESSINGCOMPOSITION AND PROCESS COMPRISING CYSTEINE AND AN ALDEHYDE BISULFITE 26Claims, No Drawings US. Cl 96/50, 96/66, 96/66.3 Int. Cl G03c 5/26, G03c5/30 Field of Search 96/66.3,

[5 6] References Cited UNITED STATES PATENTS 2,124,159 7/1938 Weyde96/61 2,902,367 9/1959 Welliver et al.. 96/66.4 3,128,180 4/1964 Henn etal. 96/66.4

Primary Examiner-Norman G. Torchin Assistant Examiner-Mary F. KelleyAttorneys-Bernard D. Wiese, W. H. J. Kline and Myron B.

Kurtzman PIIOTOGRAPI-IIC PROCESSING COMPOSITION AND PROCESS COMPRISINGCYSTEINE AND AN ALDEIIYDE BISULFITE BACKGROUND OF THE INVENTION 1. FIELDOF THE INVENTION This invention relates to photographic materials andtheir use. In one aspect, t, this invention relates to compositionsemployed in the development of high-contrast photographic elements. Inanother aspect, this invention relates to the process of developingexposed high-contrast photographic elements in a continuous transportprocessing machine wherein at least one processing solution comprisesnew photographic developercompositions.

2. DESCRIPTION OF THE PRIOR ART In the graphic arts field, where it isdesired to make photographic line and halftone reproductions, it iscustomary to employ emulsions having extremely high contrast. Indevelopment, the developing areas grow autocatalytically at a very highdeveloping rate to produce an extremely high contrast. Developers foruse with extremely high-contrast photographic films are quite differentin composition from typical blackand-white film developers. In order toobtain very high contrast and sharp lines, it has been a practice toformulate developers for such films from essentially hydroquinone, analkali, an alkali metal bromide and a low level of sulfite ion. The lowlevel of sulfite ion partially stabilizes the developer solution for ashort period of time and is achieved in all known commercial developersof this type by the use of an aldehyde sulfite, such as sodiumformaldehyde bisulfite, which acts as a sulfite ion buffer. Thesedeveloper solutions are generally stored in two parts since, forexample, the sodium formaldehyde bisulfite will dissociate at a high pHto give not only the desired sulfite ion but an equimolar amount offormaldehyde which will react with hydroquinone to destroy thedeveloping power.

The developer solutions for high-contrast films presently used incontinuous transport processing machines have a number of disadvantages.For example, all of the prior lithdevelopers have a relatively lowcapacity and begin to show substantial exhaustion after the developmentof a relatively small amount of lith-film and solution either discardedin commercial practice or replenished. It is also well known that thealdehyde bisulfites such as sodium formaldehyde bisulfite may cause someloss in speed, but more importantly may cause a loss in Dmax of thedeveloped image. While the prior art has disclosed good high contrastimages for normal conditions of time and temperature, it is ofparticular concern to improve the negative density and decrease lineveiling in fast access processing at high temperatures in automaticprocessing equipment, such as the Kodak Supermatic Processor. It wouldbe very desirable to have a developer solution for high-contrast filmswhich could be used in'high temperature continuous transport processingmachines without obtaining line veiling, while at the same timeobtaining a higher capacity in machine or tray processing for suchadeveloper solution.

In many instances it is advantageous to process high-contrast films bymeans of an activator solution, if the developing agent is incorporatedin the light-sensitive element. Such as activation process isparticularly desirable to provide longer tray life of processingsolution since an alkali processing solution without a developing agentwill be less subject to auto-xidation. Suitable incorporated developeremulsions have been described in French Pat. No. 1,479,090. Typicalemulsion compositions would comprise a silver chlorobromide gelatinemulsion (80 mole percent chloride) containing hydroquinone and coatedon a polyester film support to yield the following coverages: Silver 410mg. per square foot, gelatin 900 mg. per square foot and hydroquinone150 mg. per square foot. If desired, part of the gelatin may be replacedwith a synthetic vinyl polymer such as an alkyl-acrylate latex. Ourinvention is advantageously carried out with alkaline activatorsolutions which do not contain any developing agent or less developingagent than is required for full development activity.

SUMMARY OF THE INVENTION In accordance with this invention, there isprovided a novel and unobvious high-contrast processing solution whichmanifests an increase life and capacity while at the same time producingnegatives of very good image tone and image sharpness. The improvementsof the present invention are obtained by employing a processing solutioncomprising cysteine and a monoaldehyde which work synergistically toproduce the desired effects.

It is therefore an object of the present invention to provide a newhigh-contrast processing solution. A further object is to provide a newhigh-contrast developer solution which has improved keeping propertiesand also improved solution life in terms of aeration and film capacity.It is still a further object to provide a high-contrast developersolution which produces developed images showing a high Dmax, improvedtone, good image sharpness and improved edge effects. Another object ofthe invention is to provide an alkaline processing solution for thedevelopment of lith-type silver halide films which have therein one orseveral of a variety of silver halide developing agents. Other objectsof this invention will become obvious to those skilled in the art fromthat which appears hereinafter.

DESCRIPTION OF THE PREFERRED EMBODIMENTS According to an embodiment ofthis invention, there is provided an essentially bromide-free, highcontrast processing solution containing a monoaldehyde and cysteine inthe presence of a silver halide developing agent which exhibits theunexpected and unobvious properties referred to above. In the preferredembodiments of the invention, the developer solution additionallycontains an organic antifoggant.

According to another embodiment of this invention, there is provided anessentially bromide-free, high-contrast activator solution containing amonoaldehyde and cysteine for the processing of a photographic elementshaving a developing agent incorporated therein.

The monoaldehyde bisulfites which can be employed in the novel developercompositions are desirably alkali metal, lower hydrocarbyl and desirablylower aliphatic, monoaldehyde bisulfites. The monoaldehyde bisulfitesare well known as shown by Donovan et al. U.S. Pat. No. 2,313,523 issuedMar. 9, 1943, arid Kridel et al. U.S. Pat. No. 2,843,483 issued July 15,1958. Illustrative of the aldehydes bisulfites which may beadvantageously employed are sodium formaldehyde bisulfite, potassiumformaldehyde bisulfite, sodium acetaldehyde bisulfite and sodiumisobutyraldehyde bisulfite. A preferred monoaldehyde bisulfite is sodiumformaldehyde bisulfite. The concentration of the aldehyde bisulfitesuitably employed in our developer composition is from about 0.05 toabout 1.0 moles per liter of developer composition and is preferablyabout 0.3 moles per liter of developer composition.

The developing agents, which can be employed in our developing solutionscan be any of those commonly employed in the graphic arts. Useful silverhalide developing agents, for example, include dihydroxy benzene andsubstituted dihydroxy benzene's such as hydroquinone;chlorohydroquinone; bromohydroquinone; 2,3-dichlorohydroquinone; 2,5-dimethylhydroquinone; 2,3-dibromohydroquinone; [,4-dihydroxy-2-acetophenone-2,5-dimethylhydroquinone; 2,5-diethylhydroquinohe; 2,5-di-p-phenethylhydroquinone; 2,5-dibenzoylaminohydroquinone; 2,5-diacetaminohydroquinone; etc. [Esters ofsuch compounds, for example, formates and acetates can also be employed]These developing agents can be used alone or in any combination and canbe employed in airy concentration which is effective for development. Asuitable concentration for the developing agent is about 0.05 to about0.50 mole per liter of developing composition and is typically from 0.10to about 0.03 mole per liter of developer composition.

The cysteine in our novel processing comp ositibi i sT cysteine(flmercaptoalanine). As will be understood hereinafter, the use of theterm cysteine will include not only the amino acid but also itshydroha-lides. Suitable concentrations of the cysteine are from about0.1 to about 0.9 grams per liter of developer composition and preferablyabout 0.3 grams per liter of developer composition.

Our novel processing compositions generally do not employ bromides asrestrainers. In place of the bromide restrainers, we employ organicantifoggants. Should bromide, for example, potassium bromides which isnormally employed in lith developer solutions, be utilized, the improvedimage tone and improved developer activity, the higher line density, andthe improved solution life obtained are minimized. The organicantifoggants are well known as discussed, for instance, in Mees, TheTheory of the Photographic Process, 3rd Edition, (1966), p. 344-346. Ina preferred embodiment of this invention the organic antifoggants can bebenzimidazoles or indazoles. In another preferred embodiment of thisinvention, the organic antifoggants can be the nitrobenzimidazoles andnitroindazoles. Illustrative of the organic antifoggants which can beemployed in our developer solutions are: 5- nitrobenzimidazole,S-nitroindazole and 6-nitrobenzimidazole nitrate.

Suitable concentrations for the organic antifoggnats range from about0.1 to about 2.0 grams per liter of developer composition and preferablyabout 0.8 grams per liter of developer composition for fast access hightemperature processing. About one half these amounts are suitable fornormal temperature (68 F.) tray processing. The preferably organicantifoggants are the nitrosubstituted organic antifoggants.

Optimum results 1 are obtained when employing our processing compositionby maintaining the pH of the solution between about 10 and about 1 1.2.When machine processing, for example, in a machine such as KodakSupermatic Processor Model 242 optimum results are obtained bymaintaining the temperature of the processing solutions between about 90F. and 130 F. and preferably about 1 10 F. When tray precessing, thetemperature can range from about 60 to 80 F.

Our novel processing composition and activator solutions can be utilizedeither in tray processing or preferably in a continuous machineprocessing system, such as the fast access high-temperature transportmachines, wherein the high-contrast photographic element is processed bypassing through rollers or otherwise in one continuous motion bytransporting it into and out of at least one processing solution in themanner shown, for example, by U.S. Pats. Nos. 3,025,779 of Russell andKunz issued Mar. 20, 1962; 3,078,024 of Sandeson issued Feb. 19, 1963;3,122,086of Fitch issued Feb. 25, 1964; 3,149,551 of Cramer issued Feb.22, 1964; 3,156,173 of Meyer issued Nov. 10, l964;and 3,224,356 ofFleisher and Hixon issued Feb. 21, 1965. The continuous transportprocess may be described as a unidirectional" transport process. By theterm unidirectional it is understood that the photographic elements moveover all in one direction; however, the general movement would includeup and down movements, etc. to accommodate rollers, processingsolutions, etc.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that theseexamples are included merely for illustrating this invention.

EXAMPLE 1 Sheets of a high contrast chlorobromide emulsion aresensitometrically exposed to a 0.01 density step tablet. Individualsheets are developed respectively in one of developer solutions A, B, C,or D in a Kodak Supermatic Processor at 1 10F. A. Developer Compositionwithout Cysteine and Sodium Formaldehyde Bisulfite Hydroquinone 33.0grams S-nitrobenzimidazole nitrate 1.1 grams Triethylene glycol 60.0 ml.

Sodium bicarbonate 70.0 grams Potassium hydroxide 47.0 grams Sodiumsulfite 8.0 grams Trisodium phosphate (12H,0) 16.0 grams Aminoethanol4.0 grams Water to make 1.0 liter pH adjusted to 10.6

B. Developer Composition Developer Composition A+40 grams of SodiumFormaldehyde bisulfite. C. Developer Composition of the InventionDeveloped Composition A+40 grams Sodium Formaldehyde Bisulfite and 0.3grams cysteine. D. Developer Composition A+0.3 grams cysteine.

The results of processing the exposed films are summarized in table I.

TABLE 1 Effective Relative Contrast Speed (Toe Solution Developer Log EGamma Contrast) D,,,,,, D,,,,,,, Life A .00 i 5 3.7 0.04 5.2 1 Hr. B e.05 4.5 4.0 0.05 4.7 1 Hr. C .05 5.0 4.0 0.04 5.7 2 Hr. D .00 4.0 1.80.11 5.2 1 Hr.

'-'One gallon is circulated at F in Kodak Supermatic Processor Model 242(1 hr of solution life equals 12 hrs machine life when 5 gallons ofdeveloper are used).

EXAMPLE 11 This example illustrates the excellent capacity of thedeveloper solutions of the invention. A developer solution is preparedhaving the following formulations:

Sodium formaldehyde bisulfite (Pract) 50 Grams Sodium carbonate(monohydrate) 60 Grams Potassium carbonate (anhydrous) 60 Grams Sodiumphosphate (tribasic crystal) 215 Grams Sodium sulfite (anhydrous) 108Grams fi-nitrobenzimidazole nitrate 1.125 Grams Hydroquinone 33 GramsL-cystiene, free base 00.43 Grams Tri-ethylene glycol 50.6 GramsZ-aminoethanol 10 Grams Water to make 1.0 Liter Sheets of ahigh-contrast chlorobromide emulsion are sensitometrically exposed to a0.10 step tablet and processed at a rate of Zfpm. at 1 10 F. in a KodakSupermatic Processor. The results of the-tests as to capacity aresummarized in table 11.

1 Per 5 gallon container.

EXAMPLE 111 A developer composition (A) identical to that in example 11is prepared. A similar solution (B) is prepared except cysteine.

Strips of a high-contrast chlorobromide emulsion are exposed to a 0.1density step tablet and tray processed to simulate machine conditions at1 F. in the developer solutions. The results of the sensitometric testsare summarized in table Ill.

This example illustrates the exceptional capacity of our developercomposition over prior art developer composition when employed in trayprocessing.

Thet-high-contrast developer compositions are prepared as follows:

A.- Developer Composition Containing Cysteine and Sodium FormaldehydeBisulfite Sodium formaldehyde bisulfite (practical) 40 grams/l Sodiumcarbonate (monohydrate, granular) 60 grams/l Potassium carbonate(anhydrous) 60 grams/l Sodium phosphate (tribasic. crystal) 30 grams/lSodium sulfite (anhydrous) 4 grams/lS-Nitrobenzimiclazole 0.26 grams/l5-Nitroindazole 0.04 grams/l Boric acid 3 grams]! Hydroquinone 20 grams]L-Cysteine free base (6 mercaptoalanine) 0.33 grams/l 2.5-Dithioburea0J0 grams/l Water to make |.0 liter B. Prior Art (Lith Type Developers)Sodium formaldehyde bisulfite 70 grams/I Hydroquinone grams]! Sodiumcarbonate (monohydrate) 75 grams/l Potassium bromide 3 grams/l Water tomake 1 liter C. Prior Art (Copy Line Developer) Sodium formaldehydebisulfite 50 grams/l Hydroquinone I5 grams/I Sodium carbonatetmonohydratei grams]! Potassium bromide 0.l grams/l Water to make 1liter Test exposures of line reflection originals were made in a copycamera using 1,200 foot-candles incident illumination to produce linenegatives on a high-contrast chlorobromide emulsion. The results of thecapacity tests are summarized in table IV and the sensitometric testsare summarized in table V.

A suitable alkaline activator solution according to the inventionprovides for excellent quality of developed images in high-contrastemulsions containing incorporated developing agent. Such activatorsolutions have excellent keeping and exhaustion characteristics whencompared to developing solutions containing reducing agents. Sinceproblems with keeping are reduced, activator solutions may be preparedwhich have higher pl-ls which desirably shorten the processing time.Further, such solutions may be used at elevated temperatures with lessdeterioration on keeping. An example of the use of an activator solutionof our invention at high temperature in machine processing is givenbelow: A solution was prepared to contain:

Sodium formaldehyde bisulfite 40.0 g Sodium carbonate 600 g Potassiumcarbonate 60.0 g Sodium phosphate 30.0 g S-Nitrobenzimidazolc L2 gS-Nittoindazole 0.45 g L-cysteine 0.8 g 2-5 Dithiobiurea Water to make1.0 liter pH about I 1.8

The activator was used in a Kodak Supermatic Processor to process ahigh-contrast silver chlorobromide film containing incorporatedhydroquinone developing agent. The processing was carried out at ll0 F.at 3 f.p.m. The activator solution was used for processing sheets offilm containing typical negatives having at least percent of the areaexposed. Very good results were obtained with the activator, even after1,000 square feet of film had been processed in only 5 gallons of theactivator. Data below show the sensitometric results on sheets of filmafter various amounts of film were processed.

Exhaustion Relative Rate Speed Dmax Dmin Quality Fresh 0 3 8 0.05Excellent 200 ft 0 3.6 0.05 Excellent 400 ft 0.05 3.5 0.05 Excellent 600ft 0.05 3.6 0.05 Excellent 800 ft" -0.l0 3.4 0.05 Excellent L000 ft' 0.10 3.4 0.05 Very Good The results illustrates the excellent exhaustioncharacteristics of the activator. The exhaustion characteristics areobtained with very little change in speed and only minor change inD,,,,,,.

EXAMPLE VI A suitable activator solution for tray processing at roomtemperature, of an incorporated developer lith emulsion may Sheets ofexposed lith film comprising a high contrast chlorobromide emulsioncontaining norbornene hydroquinone developing agent were processed for30 seconds at 68 F. in shallow trays containing the above solution.Excellent quality and density resulted. When a comparison test was runusing a similar activator from which the cysteine had been eliminated,lower densities and poorer line quality resulted.

Activator solution according to our invention may be prepared as aworking solution or in more concentrated form as a liquid within thesolubility limits of the chemicals involved. Successful concentrationshave been prepared for 1:3 dilution with water.

The high-contrast emulsion processed with the processing solutions ofthis invention may be unwashed or washed to remove soluble salts. In thelatter case, the soluble salts may be removed by chill-setting andleaching or the emulsion may be coagulation washed, e.g. by theprocedures described in l-lewitson et al. U.S. Pat. No. 2,618,556 issuedNov. 18, 1952; Yutzy et al. U.S. Pat. No. 2,614,928 issued Oct 21, 1952;Yackel U.S. Pat. No. 2,565,418 issued Aug. 21, 1951, Hart et a1. U.S.Pat. No. 3,241,969 issued Mar. 22, 1966 and Waller et al. U.S. Pat. No.2,489,341 issued Nov. 29, 1949.

The emulsions processed with the processing solutions of .this inventionmay be sensitized with chemical sensitizers, such as with reducingagents; sulfur, selenium or tellurium compounds; gold, platinum orpalladium compounds; or combinations of these. Suitable procedures aredescribed in Sheppard et al. U.S. Pat. No. 1,623,499 issued Apr. 5,1927; Me- Veigh U.S. Pat. No. 3,297,447 issued Jan. 10, 1967; Waller etal. U.S. Pat. No. 2,399,083issued Apr. 23, 1946; and Dunn U.S. Pat. No.3,297,446 issued Jan. 10, 1967.

The high-contrast emulsions and other hardenable layers processed in theprocessing solutions of this invention can be hardened by variousorganic or inorganic hardeners, alone or in combination, such as thealdehydes, and blocked aldehydes, ketones, carboxylic and carbonic acidderivatives, sulfonate esters sulfonyl halides and vinyl sulfonylethers, active halogen compounds, expoxy compounds, aziridines, activeolefins, isocyanates, carbodiimides, mixed function hardeners andpolymeric hardeners such as oxidized polysaccharides like dialdehydestarch and oxyguargum and the like.

The high-contrast emulsions and elements employed in the practice ofthis invention can contain various colloids alone or in combination asvehicles, binding agents and various layers. Suitable hydrophilicmaterials include both naturally occurring substances such as proteins,for example, gelatin, gelatin derivatives, cellulose derivatives,polysaccharides such as dextran, gum arabic and the like; and syntheticpolymeric substances such as water soluble polyvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like The high-contrastemulsions and other layers of the highcontrast elements employed in thepractice of this invention can also contain alone or in combination withhydrophilic. water permeable colloids, other synthetic polymericcompounds such as dispersed vinyl compounds such as in latex form andparticularly those which increase the dimensional stability of thephotographic materials. Suitable synthetic polymers include thosedescribed, for example, in Nottorf US. Pat. No. 3,142,568issued July 29,1964; White U.S. Pat. No. 3,193,386issued July 6, 1965; Houck et al.U.S. Pat No. 3,062,674 issued Nov. 6, 1962; Houck et al. U.S. Pat. No.3,220,844 issued Nov. 30, 1965; Ream et al. U.S. Pat No. 3,287,289issuedNov. 22, 1966; Dykstra U.S. Pat No. 3,411,911 issued Nov. 19, 1968;particularly effective are those water-insoluble polymers of alkylacrylates and methacrylates, acrylic acid, sulfoalkyl acrylates ormethacrylates, those which have cross-linking sites which facilitatehardening or curing, those having recurring sulfobetaine units asdescribed in Dykstra Canadian Pat. No. 774,054.

The high-contrast elements processed in the presence of the novelprocessing solutions of this invention may contain antistatic orconducting layers, such layers may comprise soluble salts, e.g.chlorides, nitrates, etc., evaporated metal layers, ionic polymers suchas those described in Minsk US Pat. No. 2,861,056 issued Nov. 18, 1958,and Sterman et a1 U.S. Pat. No. 3,206,312 issued Sept. 14, 1965, orinsoluble inorganic salts such as those described in Trevoy U.S. Pat.No. 3,428,451 issued Feb. 18,1969.

The high-contrast elements and other layers processed in the processingsolutions of this invention can be coated on a wide variety of supports.Typical supports include cellulose nitrate film, cellulose ester filmpoly (vinyl acetal) film, polystyrene film, poly (ethyleneterephthalate) film, polycarbonate film and related films or resinuousmaterials, as well as glass, paper, metal and the like. Typically, aflexible support is employed, especially a paper support, which can bepartially acetylated or coated with baryta and/or an alphaolefm polymer,particularly a polymer of an alpha-olefin containing two to ten carbonatoms such as polyethylene, polypropylene, ethylenebutene copolymers andthe like.

The high-contrast elements and other layers processed in the processingsolutions of this invention can contain plasticizers and lubricants suchas polyalcohols, e.g. glycerin and diols of the type described in Miltonet a1. U.S. Pat. No. 2,960,404 issued Nov. 1, 1966; fatty acids oresters such as those described in Robijns U.S. Pat. No. 2,588,765 issuedMar. 11, 1952 and Duane U.S. Pat. No. 3,121,060 issued Feb. 11, 1964;and silicone resins such as those described in Du- Pont British Pat. No.955,061.

The high-contrast elements and other layers employed in the practice ofthis invention may contain surfactants such as saponin; anioniccompounds such as the alkyl aryl sulfonates described in Baldsiefen U.S.Pat. No. 2,600,831 issued June 17, 1962; amphoteric compounds such asthose described in Ben-Ezra U.S. Pat. No. 3,133,816 issued May 19, 1964;and water soluble adducts of glycidol and an alkyl phenol such as thosedescribed in Olin Mathieson British Pat. No. 1,002,878.

The high-contrast elements and other layers employed in the practice ofthis invention may contain matting agents such as starch, titaniumdioxide, zinc oxide, silica, polymeric beads including beads of the typedescribed in .lelley et al. U.S. Pat. No. 2,992,101 issued July 11,1961, and Lynn U.S. Pat. No. 2,701,245 issued Feb. 1, 1955.

The high-contrast elements and other layers employed in this inventionmay contain brightening agents including stilbenes, triazines, oxazolesand coumarin brightening agents. Water soluble brightening agents may beused such as those described in Albers et al. German Pat. No. 972,067andMc- Fall et al. U.S. Pat. No. 2,933,390 issued Apr. 19, 1960, ordispersions of brighteners may be used such as those described in.lansen German Pat. No. 1,150,274, Oetiker et al. U.S. Pat. No.3,406,070 issued Oct. 15, 1968, and Heidke French Pat. No. 1,530,244.

Spectral-sensitizing dyes can be used conveniently to confer additionalsensitivity to the light-sensitive silver halide emulsion of themultilayer photographic elements processed in the processing solutionsof the invention. For instance, additional spectral sensitization can beobtained by treating the emulsion with a solution of a sensitizing dyein an organic solvent or the dye may be added in the form ofa dispersionas described in Owens et al. British Pat. No. 1,154,781. For optimumresults, the dye may either by added to the emulsion as a final step orat some earlier stage.

Sensitizing dyes useful in sensitizing such emulsions are described, forexample, in Brooker et al. U.S. Pat. No. 2,526,632 issued Oct. 24, 1950;Sprague U.S. Pat. No. 2,503,776 issued Apr. 11, 1950; Brooker et al.U.S. Pat. No. 2,493,748 issued Oct. 10, 1950; and Taber et al. U.S. Pat.No. 3,384,486 issued May 21, 1968. Spectral sensitizers which can beused include the cyanines, merocyanines, complex (trior tetranuclear)merocyanines, complex (trior tetranuclear) cyanines, holopolar cyanines,styryls, hemicyanines (e.g. enamine hemicyanines), oxonols andhemioxonols.

Dyes of the cyanine classes may contain such basic nuclei as thethiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles,selenazoles and imidazoles. Such nuclei may contain alkyl, alkylene,hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl, and enamine groupsand may be fused to carbocyclic or heterocyclic ring systems eitherunsubstituted or substituted with halogen, phenyl, alkyl. haloalkyl,cyano, or alkoxy groups. The dyes may be symmetrical or unsymmetricaland may contain alkyl, phenyl, enamine or heterocyclic substituents onthe methine or polymethine chain.

The merocyanine dyes may contain the basic nuclei mentioned above aswell as acid nuclei such as thiohydantoins, rhodanines,oxazolidendiones, thiazolidenedions, barbituric acids, thiazolineones,and malononitrile. These acid nuclei may be substituted with alkyl,alkylene, phenyl, carboxyalkyl,

sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups, or

. heterocyclic nuclei. Combinations of these dyes may be used,

fonic acids as described in Mel-"all et a1. U.S. Pat. No. 2,933,390issued Apr. 19, 1960, and Jones et a1. U.S. Pat. No. 2,937,089 issuedMay 17, 1960.

The high-contrast elements and other layers processed in the processingsolutions of this invention can contain light-absorbing materials andfilter dyes such as those described in Sawdey U.S. Pat. No. 3,253,921issued May 31, 1966, Gasper U.S. Pat. No. 2,274,782 issued Mar. 3, 1942;Silberstein et al. U.S. Pat. No. 2,527,583 issued Oct. 31, 1950; andVanCampen U.S. Pat. No. 2,956,879 issued Oct. 18, 1960. If desired, thedyes can be mordanted, for example, as described in Jones et al. U.S.Pat. No. 3,282,699 issued Nov. 1, 1966.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

1 claim:

1. An essentially bromide-free photographic developer compositioncomprising:

a. a silver halide developing agent,

b. cysteine, and

c. a monoaldehyde bisulfite.

2. The composition of claim 1 which additionally comprises an organicantifoggant.

3. The composition of claim 2, said composition being as aqueoussolution.

4. The composition of claim 3 wherein said developing agent is presentin a concentration of from about 0.05 to about 0.50 mole per liter ofdeveloper composition, said cysteineis present in a range of from about0.1 to about 0.9 grams per liter of developer composition, said aldehydebisulfite is present in a range of from about 0.05 to about 1.0 molesper liter of developer composition and said organic antifoggant ispresent in a range of from about 0.1 to about 2.0 grams per liter ofdeveloper composition.

5. The composition of claim 2 wherein said developing agent is adihydroxybenzene developing agent and said monoaldehyde bisulfite is aformaldehyde bisulfite 6. The composition of claim 5 wherein saiddihydroxybenzene developing agent is hydroquinone, said formaldehydebisulfite is sodium formaldehyde bisulfite and said organic antifoggantis a nitro-sustituted organic antifoggant.

7. The composition of claim 6 wherein said nitrosubstituted organicantifoggant is one of 5-nitroindazole, 5- nitrobenzimidazole andS-nitrobenzimidazole nitrate.

8. The composition of claim I wherein the pH IS in a range of from about10 to about 11.2 and additionally comprises free sultite in the range offrom about 2 to about 40 grams per liter of developer composition.

9. The composition of claim 6 wherein said hydroquinone is present in aconcentration of about 0.3 mole per liter of developer composition, saidcysteine is present in a concentration of about 0.003 mole per liter ofdeveloper composition,

said sodium formaldehyde bisulfite is present in a concentration ofabout 0.3 mole per liter of developer composition and said organicantifoggant is present in a concentration of about 0.005 mole per literof developer composition.

10 in a continuous unidirectional fast access high-temperature transportprocess for developing and processing an exposed. high-contrastphotographic silver halide element, the improvement comprisingdeveloping said element in a liquid developer composition comprising:

a. a silver halide developing agent,

b. cysteine, and

c. a monoaldehyde bisulfite.

11. In a continuous process of claim 10 wherein said developercomposition additionally comprises an organic antifo gant.

1%. In a continuous process of claim 11 wherein said developercomposition is in the form ofan aqueous solution.

13. In a continuous process of claim 12 wherein said developing agent ispresent in a range in a concentration of from about 0.05 to about 0.50mole per liter of developer composition, said cysteine is present in arange of from about 0.1 to about 0.9 grams per liter of developercomposition, said aldehyde bisulfite is present in a range of from about0.05 to about 1.0 moles per liter of developer composition and saidorganic antifoggant is present in a range of from about 0.1 to about 2.0grams per liter of developer composition.

14. In a continuous process of claim 13 wherein said developing agent isa dihydroxybenzene developing agent and said monoaldehyde bisulfite is aformaldehyde bisulfite.

15. In a process of claim 14 wherein said dihydroxybenzene developingagent is hydroquinone, said formaldehyde bisulfite is sodiumformaldehyde bisulfite and said organic antifoggant is anitro-substituted organic antifoggant.

16. The process of claim 15 wherein said nitrosubstituted organicantifoggant is one of 5-nitroindazole, 5- nitrobenzimidazole,o-nitrobenzimidazole nitrate or 5- nitrobenzimidazole nitrate.

17. The process of claim 12 wherein said developing composition is at apH of about 10 to about 1 1.2 and comprises from about 2 to about 40grams per liter ofa free sulfite.

18. The process of claim 10 wherein said photographic element comprisesa silver halide emulsion in which the halide comprises at least 60 molepercent chloride.

19 The process of claim 15 wherein said hydroquinone is present in theconcentration of about 0.3 mole per liter of developer composition, saidcysteine is present in a concentration of about 0.003 mole per liter ofdeveloper composition, said sodium formaldehyde bisulfite is present ina concentration of about 0.3 mole per liter of developer composition andsaid organic antifoggant is present in a concentration of about 0.005mole per liter of developer composition.

20. The process of claim 10 wherein said photographic element istransported by rollers.

21. In a process of processing an exposed, high-contrast photographicelement, the improvement comprising developing said element in a liquiddeveloper composition comprising:

a. a silver halide developing agent,

b. cysteine, and

c. a monoaldehyde bisulfite.

22. The process of claim 21 where said developer compositionadditionally comprises an organic antifoggant and said monoaldehydebisulfite is sodium formaldehyde bisulfite.

23. An essentially bromide-free alkaline photographic activator solutioncomprising a monoaldehyde bisulfite, bisulfite, cystine and at least oneorganic antifoggant.

24. An alkaline photographic activator solution of claim 23 wherein saidorganic antifoggant is nitrosubstituted and said monoaldehyde bisulfite18 sodium formaldehyde bisulfite.

25. In a method of processing an exposed gelatino photographic silverhalide, element said element containing a silver halide developingagent, the improvement comprising processing said element in thepresence of an activator solution ofclaim 21.

26. In a method of processing an exposed gelatino photographic silverhalide element, said element containing a silver halide developingagent, the improvement comprising processing said element in thepresence of an activator solution ofclaim 24.

2. The composition of claim 1 which additionally comprises an organicantifoggant.
 3. The composition of claim 2, said composition being anaqueous solution.
 4. The composition of claim 3 wherein said developingagent is present in a concentration of from about 0.05 to about 0.50mole per liter of developer composition, said cysteine is present in arange of from about 0.1 to about 0.9 grams per liter of developercomposition, said aldehyde bisulfite Is present in a range of from about0.05 to about 1.0 moles per liter of developer composition and saidorganic antifoggant is present in a range of from about 0.1 to about 2.0grams per liter of developer composition.
 5. The composition of claim 2wherein said developing agent is a dihydroxybenzene developing agent andsaid monoaldehyde bisulfite is a formaldehyde bisulfite.
 6. Thecomposition of claim 5 wherein said dihydroxybenzene developing agent ishydroquinone, said formaldehyde bisulfite is sodium formaldehydebisulfite and said organic antifoggant is a nitro-sustituted organicantifoggant.
 7. The composition of claim 6 wherein said nitrosubstitutedorganic antifoggant is one of 5-nitroindazole, 5-nitrobenzimidazole and5-nitrobenzimidazole nitrate.
 8. The composition of claim 1 wherein thepH is in a range of from about 10 to about 11.2 and additionallycomprises free sulfite in the range of from about 2 to about 40 gramsper liter of developer composition.
 9. The composition of claim 6wherein said hydroquinone is present in a concentration of about 0.3mole per liter of developer composition, said cysteine is present in aconcentration of about 0.003 mole per liter of developer composition,said sodium formaldehyde bisulfite is present in a concentration ofabout 0.3 mole per liter of developer composition and said organicantifoggant is present in a concentration of about 0.005 mole per literof developer composition.
 10. In a continuous unidirectional fast accesshigh-temperature transport process for developing and processing anexposed, high-contrast photographic silver halide element, theimprovement comprising developing said element in a liquid developercomposition comprising: a. a silver halide developing agent, b.cysteine, and c. a monoaldehyde bisulfite.
 11. In a continuous processof claim 10 wherein said developer composition additionally comprises anorganic antifoggant.
 12. In a continuous process of claim 11 whereinsaid developer composition is in the form of an aqueous solution.
 13. Ina continuous process of claim 12 wherein said developing agent ispresent in a range in a concentration of from about 0.05 to about 0.50mole per liter of developer composition, said cysteine is present in arange of from about 0.1 to about 0.9 grams per liter of developercomposition, said aldehyde bisulfite is present in a range of from about0.05 to about 1.0 moles per liter of developer composition and saidorganic antifoggant is present in a range of from about 0.1 to about 2.0grams per liter of developer composition.
 14. In a continuous process ofclaim 13 wherein said developing agent is a dihydroxybenzene developingagent and said monoaldehyde bisulfite is a formaldehyde bisulfite. 15.In a process of claim 14 wherein said dihydroxybenzene developing agentis hydroquinone, said formaldehyde bisulfite is sodium formaldehydebisulfite and said organic antifoggant is a nitro-substituted organicantifoggant.
 16. The process of claim 15 wherein said nitrosubstitutedorganic antifoggant is one of 5-nitroindazole, 5-nitrobenzimidazole,6-nitrobenzimidazole nitrate or 5-nitrobenzimidazole nitrate.
 17. Theprocess of claim 12 wherein said developing composition is at a pH ofabout 10 to about 11.2 and comprises from about 2 to about 40 grams perliter of a free sulfite.
 18. The process of claim 10 wherein saidphotographic element comprises a silver halide emulsion in which thehalide comprises at least 60 mole percent chloride. 19 The process ofclaim 15 wherein said hydroquinone is present in the concentration ofabout 0.3 mole per liter of developer composition, said cysteine ispresent in a concentration of about 0.003 mole per liter of developercomposition, said sodium formaldehyde bisulfite is present in aconcentration of about 0.3 mole per liter of developer composition andsaid organic antifoggant is present in a concentration of about 0.005mole per liter of developer composition.
 20. The process of claim 10wherein said photographic element is transported by rollers.
 21. In aprocess of processing an exposed, high-contrast photographic element,the improvement comprising developing said element in a liquid developercomposition comprising: a. a silver halide developing agent, b.cysteine, and c. a monoaldehyde bisulfite.
 22. The process of claim 21where said developer composition additionally comprises an organicantifoggant and said monoaldehyde bisulfite is sodium formaldehydebisulfite.
 23. An essentially bromide-free alkaline photographicactivator solution comprising a monoaldehyde bisulfite, cystine and atleast one organic antifoggant.
 24. An alkaline photographic activatorsolution of claim 23 wherein said organic antifoggant isnitrosubstituted and said monoaldehyde bisulfite is sodium formaldehydebisulfite.
 25. In a method of processing an exposed gelatinophotographic silver halide element, said element containing a silverhalide developing agent, the improvement comprising processing saidelement in the presence of an activator solution of claim
 21. 26. In amethod of processing an exposed gelatino photographic silver halideelement, said element containing a silver halide developing agent, theimprovement comprising processing said element in the presence of anactivator solution of claim 24.